EP0475123B1 - Utilisation de 2-n-alkyle-1,2-benzisothiazolin-3-ones comme microbiocides techniques - Google Patents

Utilisation de 2-n-alkyle-1,2-benzisothiazolin-3-ones comme microbiocides techniques Download PDF

Info

Publication number
EP0475123B1
EP0475123B1 EP91113817A EP91113817A EP0475123B1 EP 0475123 B1 EP0475123 B1 EP 0475123B1 EP 91113817 A EP91113817 A EP 91113817A EP 91113817 A EP91113817 A EP 91113817A EP 0475123 B1 EP0475123 B1 EP 0475123B1
Authority
EP
European Patent Office
Prior art keywords
benzisothiazolin
alkyl
use according
general formula
ones
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91113817A
Other languages
German (de)
English (en)
Other versions
EP0475123A1 (fr
Inventor
Wolfgang Dr. Lindner
Gerhard Dr. Wöhner
Wolfgang Dr. Schaper
Burkhard Dr. Sachse
Peter Dr. Hartz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell Riedel de Haen AG
Original Assignee
Riedel de Haen AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Riedel de Haen AG filed Critical Riedel de Haen AG
Publication of EP0475123A1 publication Critical patent/EP0475123A1/fr
Application granted granted Critical
Publication of EP0475123B1 publication Critical patent/EP0475123B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the invention relates to the use of 2-n-alkyl-1,2-benzisothiazolin-3-ones as technical microbicides.
  • Microbiocidal substances are therefore added to these materials to maintain their value, although the environmental compatibility or toxicology of the agents used has so far been neglected. Chlorinated phenols and tributyltin esters have therefore been used essentially. For ecological reasons, however, the use of these substances must be restricted. There is therefore a great need for water-insoluble, non-volatile, broadly antifungal, less toxic and less harmful to the environment, which are used to protect wood, leather, textiles, paints, plaster, technical aqueous formulations, paper, roof coatings, Plastics, etc. can be used.
  • 2-alkyl-4-isothiazolin-3-ones have already been proposed for the fungicidal treatment of industrial materials.
  • 2-n-octyl-isothiazolin-3-one is used to protect facade paints, leather, wood, etc. It is disadvantageous that this compound is not stable to alkali and is hydrolyzed at pH values above 9 and is therefore inactivated. In addition, it is easily washed out of the material to be protected by rainwater, so that the protection is not as long as desired.
  • the object of the present invention is to provide compounds which have long-lasting high fungicidal activity, can be used in technical systems without adversely affecting their properties and which at the same time no longer have the disadvantages mentioned above.
  • the compounds of general formula I to be used according to the invention are notable for high activity and their broad spectrum of activity against yeasts, such as e.g. Candida albicans, Torula utilis, Saccharomyces cerevisiae, molds, such as e.g. Cladosporium resinae, Aspergillus niger, Sclerophoma pityophila, Scopulariopsis brevicaulis or wood-fading fungi, e.g. Aureobasidium pullulans from. They are therefore outstandingly suitable for protecting technical materials against fouling with fungi and yeasts, have a significantly higher activity against mold and are much more resistant to leaching than the N-alkyl-1,2-benzisothiazoline described so far for this application.
  • the compounds of general formula I can also be used in fields of application, such as, for example, in coatings on extremely alkaline concrete substrates with high wash-out loads, in which the 2-octylisothiazolin-3-one corresponding to the prior art is hydrolyzed and ineffective. They can therefore be particularly advantageous in materials such as facade coatings, roof tile coatings, cooling lubricants, silicate paints and other alkaline technical systems can be used as fungicides.
  • a crop protection fungicide is expected to have selective activity and good degradability, while a fungicide should be as broadly effective as possible for technical products and should in part protect the materials over several years.
  • Preferred formulations are solutions, but aqueous emulsions or water-dilutable emulsion concentrates are also advantageous.
  • the choice of solvent for solutions is not critical.
  • Aromatic petrol, xylene, trimethylbenzene are particularly suitable for non-polar systems; Ketones such as acetone, cyclohexanone, isophorone, methyl isobutyl ketone; Ethers and glycol ethers, such as, for example, diisopropyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether; Esters such as, for example, ethyl acetate, butyl acetate; Glycols, their mono- and diethers or their mono- or diesters.
  • the formulations contain the compounds of the general formula I preferably in amounts of 1 to 98% by weight, particularly preferably in amounts of 10 to 50% by weight.
  • the application concentration depends on the type of material to be protected, the leaching load and the microbial contamination to be expected and is preferably between 0.005 and 3%, particularly preferably between 0.05 and 1%, based on the material to be protected.
  • a particularly advantageous use according to the invention is the protection of plastics containing polyvinyl chloride from attack by Scopulariopsis brevicaulis.
  • This fungus preferably grows on polyvinyl chloride and is able to reductively form phosphate plasticizers, phosphine, arsenic compounds arsan and antimony compounds stilban (Richardsen, Guernsey).
  • Phosphorus, arsenic and antimony compounds are often used as stabilizers, e.g. added as flame retardant PVC. Since the corresponding hydrogen compounds are highly toxic, fouling with Scopulariopsis brevicaulis must be prevented.
  • the compounds of the general formula I are outstandingly suitable for this purpose, since they are highly active against Scopulariopsis brevicaulis and are not destroyed by the temperature loads which occur during the calendering of the plastics.
  • Another advantageous use according to the invention is the use in non-polar, hydrophobic media, such as e.g. Textile waterproofing agents, silicone oils or petrol. 2-Octylisothiazolin-3-one cannot be used in these media.
  • the compounds of general formula I can also be used in combination with other known antimicrobial substances.
  • examples include: benzimidazolylmethyl carbamate, quaternary ammonium acid (quats), thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, iodopropargylbutylcarbamate, 2-octyl-isothiazolin-3-one, 2-methylthio-4-tertiarybutylamino-6-cyclopropane Dichlofluanid, captan, folpet.
  • benzimidazolylmethyl carbamate quaternary ammonium acid (quats)
  • thiocyanatomethylthiobenzothiazole methylene bisthiocyanate
  • iodopropargylbutylcarbamate 2-octyl-isothiazolin-3-one
  • the microbicidal effectiveness is determined by determining the minimum inhibitory concentration (MIC values).
  • the MIC value indicates the lowest concentration of an active ingredient at which the growth of the test germ is still completely inhibited.
  • graduated amounts of active ingredient are dissolved in liquid culture media at 50 ° C, the culture media are then solidified by cooling, infected with the test strains and incubated.
  • a modified method of testing the bacteriostatic effect using the dilution test is therefore used (cf. guidelines for testing chemical disinfectants, Gustav Fischer Verlag, Stuttgart, 2nd edition, 1969, pages 5-6).
  • the color-coated test specimens (series C) were soaked in tap water for 96 hours, using 63 l of water per m2. The leaching water was changed every 24 hours.
  • the active substances to be tested are incorporated in graded concentrations in a commercially available styrene acrylate paint.
  • the biological test is carried out on round filter paper (No. 597 from Schleicher & Schüll, diameter 5.5 cm). For this purpose, the filters were coated on one side with the modified emulsion paint to be tested.
  • a fresh concrete was made by mixing 71.6% screed sand (approx. 1.6% moisture), 18.9% Portland cement according to DIN 1164 and 9.6% tap water, which was filled into a petri dish and the surface with the spatula was smoothed.
  • the concrete is compacted by tapping the petri dish carefully.
  • the freshly painted paper filters are immediately placed on the freshly made moist concrete and pressed on with the help of a spatula.
  • the petri dish was sealed with an adhesive tape (e.g. tape) to prevent it from drying out.
  • test specimens were then stored in a heating cabinet at 60 ° C. for 48 hours. The mixture was then allowed to cool to room temperature and then the moist filter was carefully lifted off the concrete surface with the spatula. The filters were then air dried on filter paper for 16 hours. To simulate leaching by rainwater, the test specimens coated with paint were watered with tap water for 48 hours (series "loaded” in the table), 60 l water per m2 being used. The leaching water was changed every 24 hours.
  • dioctyl phthalate was mixed with 4% 2-n-octyl-1,2-benzisothiazolin-3-one and heated to 200 ° C. for 15 minutes to simulate the temperature during the manufacture of PVC films.
  • Freshly tanned leather (wet blue) was immersed in aqueous baths, each containing 0.01% of the fungicides to be tested.
  • the fungicidal effect is on the leather sections tested on solid nutrient media according to ASTM D 4576 and evaluated according to the scheme given there on a scale from 0 to 4.

Claims (6)

  1. Utilisation de 2-n-alkyl-1,2-benzisothiazoline-3-ones de formule générale I
    Figure imgb0004
     dans laquelle R est un radical alkyle en C₆-C₈ à chaîne droite, en tant que microbicides techniques.
  2. Utilisation selon la revendication 1, pour protéger des revêtements de façades, des revêtements de tuiles, des lubrifiants-réfrigérants, des peintures aux silicates et d'autres systèmes techniques alcalins, ainsi que pour la protection du bois, du cuir, des semi-produits à base de cuir, des peintures pour façades, des systèmes d'enduits, des peintures sur bois, des plastiques tels que le PVC, des polyuréthannes ou du polybutylène, des enduits plastiques, des textiles, des circuits fermés d'eaux industrielles, des masses d'étanchéité siliconées, des fluides d'usinage des métaux, des colles et des carburants.
  3. Utilisation selon les revendications 1 et/ou 2, caractérisée en ce que le PVC est protégé contre une infestation par Scopulariopsis brevicaulis.
  4. Utilisation selon l'une ou plusieurs des revendications 1 à 3, caractérisée en ce que le composé de formule I est utilisé à des concentrations de 0,005 à 3 % et tout particulièrement de 0,05 à 1 % par rapport au matériau à protéger.
  5. Utilisation selon l'une ou plusieurs des revendications 1 à 4, caractérisée en ce que le composé de formule générale I est utilisé sous forme d'une solution.
  6. Utilisation selon l'une ou plusieurs des revendications 1 à 5, caractérisée en ce que le composé de formule générale I est utilisé en combinaison avec d'autres matières actives antimicrobiennes.
EP91113817A 1990-08-30 1991-08-17 Utilisation de 2-n-alkyle-1,2-benzisothiazolin-3-ones comme microbiocides techniques Expired - Lifetime EP0475123B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4027378A DE4027378A1 (de) 1990-08-30 1990-08-30 Verwendung von 2-n-alkyl-1,2-benzisothiazolin-3-onen als technische mikrobiozide
DE4027378 1990-08-30

Publications (2)

Publication Number Publication Date
EP0475123A1 EP0475123A1 (fr) 1992-03-18
EP0475123B1 true EP0475123B1 (fr) 1995-01-04

Family

ID=6413193

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91113817A Expired - Lifetime EP0475123B1 (fr) 1990-08-30 1991-08-17 Utilisation de 2-n-alkyle-1,2-benzisothiazolin-3-ones comme microbiocides techniques

Country Status (5)

Country Link
EP (1) EP0475123B1 (fr)
AT (1) ATE116522T1 (fr)
DE (2) DE4027378A1 (fr)
ES (1) ES2069142T3 (fr)
GR (1) GR3015576T3 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9304903D0 (en) * 1993-03-10 1993-04-28 Zeneca Ltd Compounds,preparation and use
DE4403838A1 (de) * 1994-02-08 1995-08-10 Bayer Ag 1,3,2-Benzodithiazol-1-oxid-Derivate
GB9500856D0 (en) * 1995-01-17 1995-03-08 Zeneca Ltd Composition and use
DE19704158A1 (de) * 1997-02-04 1998-08-06 Fischer Artur Werke Gmbh Polyurethanzusammensetzung mit verbesserter langzeitresistenz gegen Mikroorganismenbefall
EP1072192A1 (fr) * 1999-07-27 2001-01-31 Basf Aktiengesellschaft Polyuréthanes thermoplastiques
GB0012786D0 (en) 2000-05-26 2000-07-19 Avecia Ltd Method and compositions
DE10218482A1 (de) * 2002-04-25 2003-11-20 Sto Ag Mittel zur Behandlung von mit Algen und/oder Pilzen befallenen Flächen
DE102005044855A1 (de) * 2005-09-21 2007-03-29 Clariant Produkte (Deutschland) Gmbh Biozide Zusammensetzungen
CN112409637A (zh) * 2020-11-12 2021-02-26 广元瑞峰新材料有限公司 一种软质塑料专用的环保型防霉抗菌剂

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB848130A (en) * 1958-03-14 1960-09-14 Ici Ltd Benzisothiazolones
US3517022A (en) * 1967-10-03 1970-06-23 Rohm & Haas Certain 2-carbamoyl-1,2-benzisothiazolones
SE392103B (sv) * 1970-04-27 1977-03-14 Sherwin Williams Co Sett att framstella 1,2-bensisotiazolin-3-oner
US4396413A (en) * 1971-05-12 1983-08-02 Rohm And Haas Company Metal salt complexes of 3-isothiazolones as effective biocidal agents
GB1531431A (en) * 1975-01-29 1978-11-08 Ici Ltd Method for the control of micro-organisms

Also Published As

Publication number Publication date
ATE116522T1 (de) 1995-01-15
DE4027378A1 (de) 1992-03-05
GR3015576T3 (en) 1995-06-30
DE59104132D1 (de) 1995-02-16
ES2069142T3 (es) 1995-05-01
EP0475123A1 (fr) 1992-03-18

Similar Documents

Publication Publication Date Title
EP0332578B1 (fr) Composés du phoshonium avec activité biocide
EP0601674B1 (fr) Dispersion aqueuse à activité fongicide et algistatique
DE102005045129A1 (de) Zubereitung zur fungiziden und algiziden Ausrüstung alkalischer Beschichtungszusammensetzungen
EP0475123B1 (fr) Utilisation de 2-n-alkyle-1,2-benzisothiazolin-3-ones comme microbiocides techniques
WO1998025464A1 (fr) Melanges microbicides
EP0804079A1 (fr) Combinaison algicide
EP0254857B1 (fr) Utilisation des dérivés de 1-aryl-3-hydroxy-3-alkyl-4-(1,2,4-triazol-1-yl)-butane comme microbicides pour la protection des matériaux
DE2022370A1 (de) N-Fluordichlormethylthio-sulfamidsaeure-Derivate,Verfahren zu ihrer Herstellung und ihre mikrobizide und fungizide Verwendung
EP0068442A1 (fr) Agent, son application et procédé pour combattre les champignons et bacteries phytopathogeniques
WO2000059305A1 (fr) Composition microbiocide
DE2506482C3 (de) Organische Dicarbonate enthaltendes Mittel zur Bodendesinfektion und Bekämpfung von Pflanzenkrankheiten
JP4968870B2 (ja) 工業用抗菌組成物及び抗菌方法
EP0108039B1 (fr) Stannates-(IV) d'ammonium
DE2845408B2 (de) N-(2-Methyl-l-naphthyl)-maleinimid, Verfahren zu dessen Herstellung und seine Verwendung
EP0170168B1 (fr) N,N diéthyl, N'aryl N'(dichlorofluorométhylthio) sulfamide-microbiocides
DE1210620B (de) Fungitoxische Mittel
DE2538016A1 (de) Fungizide und bakterizide mittel
DD278061A1 (de) Mikrobizide mittel
JP4915830B2 (ja) 工業用抗菌組成物及び抗菌方法
JP4807717B2 (ja) 工業用抗菌組成物及び抗菌方法
DE2904390A1 (de) Verduennbare benzimidazolcarbaminsaeurealkylester-formulierung, verfahren zu ihrer herstellung und verwendung als biozid
DE2040069A1 (de) Verwendung von 2-Benzimidazolylcarbaminsaeureestern als Anstrichfungizide
DE3604791A1 (de) Mikrobizides mittel
EP0291800B1 (fr) Iodopropargyléthers de cyanhydrines, un procédé pour leur préparation et leur utilisation comme microbicides
JP4766641B2 (ja) 工業用抗菌組成物及び抗菌方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE

17P Request for examination filed

Effective date: 19920228

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HARTZ, PETER,DR.

Inventor name: SACHSE, BURKHARD, DR.

Inventor name: SCHAPER, WOLFGANG, DR.

Inventor name: WOEHNER, GERHARD, DR.

Inventor name: LINDNER, WOLFGANG, DR.

17Q First examination report despatched

Effective date: 19940214

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL SE

REF Corresponds to:

Ref document number: 116522

Country of ref document: AT

Date of ref document: 19950115

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO MILANO S.P.A.

REF Corresponds to:

Ref document number: 59104132

Country of ref document: DE

Date of ref document: 19950216

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950310

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2069142

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3015576

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010618

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010629

Year of fee payment: 11

Ref country code: AT

Payment date: 20010629

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20010725

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20010802

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010803

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20010814

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010831

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010912

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010927

Year of fee payment: 11

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020817

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020817

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020818

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020831

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020831

BERE Be: lapsed

Owner name: *RIEDEL-DE HAEN A.G.

Effective date: 20020831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030301

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030305

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020817

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030430

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030912

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050817